Polyurethane polymer containing a metallic dicyanamide



POLYURETHANE POLYMER CONTAINING A METALLIC DICYANAMIDE John Burkus, Pompton Plains, N. J., assignor to United States Rubber Company, New York, N. Y., a corpora: tion of New Jersey Application November 26, 1956 Serial No. 624,208

4 Claims. (Cl. 260-25) No Drawing.

This invention relates to rubbers of the polyesteru'rethane type, and more particularly it relates to the preservation of such rubbers against deterioration,especially by moisture and light, with the aid of a metallic dicya'namide. 5

As is well known, rubbers of the polyester-urethane 1 --,-Patented Mar. 10, 1959 However, I have now very surprisingly and unexpectedly discovered that metallic dicyanamides, when added to the polyester-urethane rubber composition, have a remarkable inhibiting effect on the degration ofsuch compositions. The metallic dicyanamides, in both'the solid and the foamed polyester-urethane rubbers greatly diminish the deteriorating effects of moisture and the discoloration by light. A particularly preferred metallic dicyanamide is sodium dicyanamide, NaN(CN) which is a commercially available material.

The invention is applicable to any conventional polyester-urethane rubber composition. The polyester used in such preparations is typically made from a glycol, for example from a mixture of ethylene and propylene glycols, and an aliphatic saturated dicarboxylic acid, for example, adipic acid, using an excess of glycol over the acid so that the, resulting polyester contains terminal alcoholic hydroxyl groups. Such polyester may be linear, or it may be branched, the latter effect being achieved by including in the preparation a trialcohol, such as trimethylolpropane or trimethylolethane. Usually such an amount of glycol is used as to give the polyester having a hydroxyl number V of 20 to 120, and preferably 3,6 to 67, and a low acid made with a polyester backbone degrade in the presence of atmospheric moisture. This deficiency has been noted in the literature (Brockhagen, Kunststoife' 44, 555-8, December 1954). As degradation progresses, the foams become softer and tend to acquire permanent set when deformed. Degradation of this type has been observed in:

samples stored on an open shelf while control samples stored in a desiccator over a drying agent did not change at all. The change in properties during shelf aging is a very serious matter, and occurs in the solid rubber as well as in foam. It has impeded large scale exploitation of polyester-urethane rubbers by the whole rubber industry in this country. I

As an example of this deterioration, a sample of polyester-urethane foam lost 15% of its original modulus during a six =month shelf aging-period and.33% of-its original modulus during .a' 15 monthperiod. The'de gradation is accelerated by an increase in temperature and/or humidity. Thus, many samples of polyester-urethane foam aged at 70 C. in an atmosphere of 95% relative humidity have been observed to lost: 1030% of their original modulus in one Week, the extent of degrada tion depending at least partly upon the catalyst used in. preparing the foamw Heating at" 70 C. over water is'a method which'is used generally throughout-the rubber industry as an accelerated aging test for polyurethane rubber.

' Exposure to light also has a definite undesirable effect on polyester-urethane rubbers. The rubbers tend to discolor, becoming extremely dark after direct exposure to ultra-violetlight for a period of time. I

I have attempted without success to forestall such degration by adding various materials tothe polyesterur et hane composition. These materials included iron oxide, barium stearate, calcium carbonate, zinc oxide, magnesium. oxide, lead carbonate, lead stearate, di'basic value less than 2 and preferably less than 1. The molecular weight of the polyester preferably ranges from 1700 to 3000. Polyester-polyamides, polyester-polyethers and polyetherglycols, having terminal alcoholic hydroxyl groups, may be used in place of part of the polyester. The polyester or the likeis reacted with a polyisocyanate, for example, triphenylmethane triisocyanate, tolylene diisocyanate, naphthalene 1,5-diisocyanate, or p,p'-diphenylmethane diisocyanate, using a considerable molar excess, commonly from a 20% to a 250% and preferably from a 50% to a 100% molar excess, of the polyisocyanate over that amount which would be required to react with all of the alcoholic hydroxyl groups furnished by the polyester. The reaction is frequently efiected by heating a mixture of the polyester, or similar high molecular weight compound having two or more alcoholic hydroxyl groups per molecule, and the polyisocyanate under anhydrous conditions at an elevated temperature, e. g. 70-150", C., to form a soluble, uncured, material which is a polyurethane having terminal isocyanate groups.

The polyisocyanates employed in preparing thepolyester-polyisocyanate product are generally diisocyanates, for example, polymethylene diisocyanates such as ethylene diisocyanate, hexam'e'thylene diisocyanate and, tetramethylene diisocyanate; alkylene diisocyanates such as propylene-1,2-diisocyanate; cycloalkylene diisocyanates aliphatic-aromatic diisocyanates such as p,p-diphenyl' methane diisocyanate, meta or para xylylene diisocyanate,

lead ste arate,barium cadmium stearate, and mica None 60 of these helped and indeedthe lead, zinc, magnesium and cadmium compounds were actually detrimental. Various organic compounds .w,er eialso .tested, but they were not beneficial.

such as 1,4-di-isocyanatocyclohexane, as well as aromatic diisocyanates such as mand p-phenylene diisocyanate toluene diisocyanate, p,p'-diphenyl diisocyanate and 1,5- naphthylene diisocyanate, in which category we include and phenylethane diisocyanate COHB ooN-on-onz-Nom isocyanate p hed to "a' trivalent hydrocarbon" radical, whether an aliphatic, aromatic, or aliphatic-arc matic. radical as in butane-1,2,2-triisocyanate, benzene-1, 3,5-triisocyanate, diphenyl-2,4,4'-triisocyanate, diphenyl-4, 6,4-triisocyanate, toluene-2,4,6-triisocyanate, ethyl benzene-2,4,6-triisocyanate and triphenylmethane 4,4, 4"- triisocyanate. Triisocyanates derived from corresponding substituted trivalent hydrocarbon radicals, such as monochlorobenzene-2,4,6-triisocyanate may also be used.

Many such polyester-polyisocyanate intermediate products hereinafter referred to as the uncured polyurethane or polyurethane intermediate, can be thus prepared in the form of liquids; others are normally solids.

In many cases it is found to be highly advantageous to include in the polyurethane elastomer preparation (in addition to the diisocyanate and the polyester), a small amount of an agent capable of forming urea linkages in the polymer. In general, such urea linkage forming agents are materials capable of condensing with the diisocyanate to yield at least one ureylene group Although such agents should be bifunctional with respect to isocyanate, i. e., possess two available active hydrogen atoms, it is not necessary that these reactive groups both be --NH groups. bining with available isocyanate groups on different molecules of the elastomer, or with available isocyanate groups on different parts of the same molecule of the elastomer thus increasing the chain length of the polymer.

suitably employed in an amount varying in specific cases from to 3.5 mole per mole of polyester used but preferably, when used at all, varying from .10 to .60 mole per mole of polyester. Examples of such reagents are (a) aromatic diamines such as p,p'-diaminodiphenyl methane, (b) aromatic aminophenols or aminoalcohols such as p-aminophenol, m-aminophenol, and p-aminobenzyl alcohol, (c) aliphatic diamines such as hexamethylenediamine, (d) aliphatic amino alcohols such as ethanolamine, (e) diamides such as adipamide or urea, and (f) water.

In the most typical practice of the foregoing modification of the invention, the addition of the ureylene linkage. forming agent is generally delayed until after the initial reaction of the diisocyanate and polyester. The treatment with the ureylene linkage forming agent is suite ably carried out while masticating the elastomer in a suitable heavy duty mixer, generally while heating the mixture (usually to a temperature of, for example, 20 to 200 C.). i

may of course also be employed as' one of the reactants under proper conditions, to serve as a ureylene linkage former,.in the above disclosed modification of the invention. If the starting materials are not substantially anhydrous, their water content should preferably be predetermined rather carefully, so that such water can be taken into account. Excess polyisocyanate is then added to correspond to this amount.

As is well known, the polyurethane intermediate containing available isocyanate groups is capable of being cured by the action of various initiators of cross-linking, usually chemicals containing two or more hydrogen atoms available for reaction with the available isocyanate groups, notably water, or organic chemicals in general containing two or more -OH and/or NI-I and/or -SH groups. Among such known curing agents may be mentioned polyamines, notably primary diamines, such as hexamethylene diamine, p-phenylene diamine, p,p'-diaminodiphenylmethane, o-dichlorobenzidine, and tolylenediamine; polyhydric alcohols, notably diols, such as butanediol; and polymercaptans such as hexamethylene dithiol. Compounds with mixed functional groups They are believed to act by com- Other modifying ingredients may be present during I the preparation.

In most cases, it is desirable to accelerate or promote the reaction between the diisocyanate and the polyester,

and this may be done with the aid of certain catalytic materials. Known catalysts for this reaction include the soluble heavy metal salts, and the tertiary amines, the

latter being preferred. Examples of such catalysts are cobalt naphthenate, triethylamine, diethyl cyclohexylamine, N-methyl morpholine, N,N'dimethyl piperazine, di-(beta-diethylaminoethyl) adipate, Z-hydroxypropyl-N- (3-dimethylaminopropyl) carbamate, and N,N'-hexamethylene di-(beta-diethylaminoethyl carbamate). Such catalysts are particularly necessary when preparing the foamed product.

The reaction of the polyester with the diisocyanate is usually carried out under substantially moisture-free conditions, although water itself in controlled amounts are also used, notably amino alcohols, such as amino ethanol and p-amino-phenylmethylcarbinol. Peroxides also have a curing effect.

When it is desired to make a foamed product, the curing agent is appropriately comprised for the most part of Water, since water is unique among the foregoing agents in causing the release of carbon dioxide gas during the cure so that the polyurethane becomes blown or expanded.

Although the cure of the polyester-polyisocyanate in.- termediate to form the elastic polyurethane proceeds at room temperature, the reaction is slow and in practice we apply heat to the mass to accelerate the cure. Thus,

The bifunctional ureylene linkage forming agents are by heating to temperatures of, for p 212 to 300 F., substantial cure can be effected in as little as 5 to 10, minutes, but if less highly elevated temperatures are employed, e. g., 125 F., longer times, such as l to 3 hours may be required to effect appreciable cure. Ex?

. posure of the mass to open steam or to steam under pressure in an autoclave is a convenient way of supplying simultaneously the water vapor required for curing as well as the elevated temperature desired to shorten the time of cure.

In some cases the synthetic elastomeric polyurethane polymer is made by reacting together in suitable fashion (1) a polyester or polyester amide, (2) a bifunctional compound like a diamine, and (3) a diisocyanate, such as naphthylene-1,5-diisocyanate or p,p-diphenylmethane' uncured elastomeric product,

diisocyanate to give an the resulting uncured reaction and eifecting curing of product by intimately admixing therewith an organic.

polyisocyanate, generally a diisocyanate identical with that previously employed, in amount sufficient to effect curing, often in amount such as to bring the total number of- -..-NCO equivalents in the cured composition to around three equivalents of -NCO per mole of polyester orpolyester' amide, and subjecting the resulting mixture to.

heat and pressure.

Instead of first preparing in a separate step an intermediate product or prepolymer from the polyester and the diisocyanate, and then adding a curing agent in a distinct subsequent step, I may blend all the desired ingredients at once. This is frequently done in preparing casting compositions for foamed-in-place elastomer.

In accordance with the invention, there is included in any of the foregoing compositions, at any convenient stage in the preparation thereof, but in any case prior to curing, a small amount of a metallic dicyanamide.

Pigments, fillers, and other compounding or modifying ingredients may also be present.

The following examples practice of the invention in more detail.

will serve to illustrate the "EXAMPLE In this example, polyester-urethane foams were made in'accordance with the following recipe:

6 a maximum temperatureof 110 C. was sometimes measured in the center of the foam. This temperature was usually reached .about five minutes after the last ingredient was added. The foams were self-curing so no additional t I v V 5 heating was used. f An alternative method which is used when larger pieces 0 y ene 61s1soyanate (mixture of 2,4 and 2,0 iso- 0 of foam are needed is as follows. Polyester is premixed i 1 I with sodium dicyanamide, Water, catalyst and Emulphor ig or T M -"r- -r- EL-719. This mixture is then supplied through a meter- (see a e "'"Q 10 ing pump to a small-volume mixing chamber containing 'Vana a rapidly rotating (about 1000 R. P. M.) internal mixer I 2 with small clearances. Tolylene diisocyanateis simul 33 1 li qge y i y a t es a o o l a taneou'sly metered in the proper proportion into the mix V 6111:0860 SfllZll 011188.118 (308.58 I Y while it is eiiig formed. C0mp%und 4 i 'lablg I) contaili ed 8 m rate of Input adlusted tqthe i two parts oleic acid in place of Emulphor Inn-719. 5 volume of the mixing chamber, so that the holdup time g, The polyester is made as follows: i Qt order of 7 seconds 3 w f Product Charge, v Moles issues from the mixer as a clear liquid. It is collected I Ad-ipi acid i 3 L0 irlilrggld's where it quickly expands andassumes the mold i igg z ggg "'T f?" The polyester-urethane foams were subjected to acceler- I "'"',1 I I ated humid aging tests. The samples tested were allowed The mixture is heated in an inert "atmospherqandwater to remain at room'te'mperatureat least a week but not is'distilled on until an acid number of ab ut jz fis' obm r t a four weeks before t Start of he' sms t s tained'." Vacuum is then applied, and excessldiethylene 2 R s lt f tests r h n m'the f lo mg Table I, gly'colis' distilled oflE until a hydroxyl number of about 60 5 which shows the loss in modulus on aging J is obtained. The reactor temperature should not be a l- Table I shows that there are var1at1ons'1n'1n1t1al softlowed to go above 230 C. The polyester has a viscosity mess with difierentcatalysts and there are also-differences of about 18,000 centipoises at f 'C. In ge'neraLany in rates of degradation in the-acceleratedhumid ag ng fluid polyester or the like with a low acid number (0-10), a test. The effect of catalyst on softness is bothsurprising and with viscosity characteristics suitable for forming a and mysterious. No explanation has been ofiered. Difstable foam, may be used. ferences in the sensitivity to moisture which result from j Thefoa'm samples used in obtaining the data'f folr Table the us of ifie e ta y y be related to the a I were made in the following manner. Fifty grarrr batches ly'st volatility, its degree of alkalinity and the nature of of polyester were weighed 'into one pint paper cups, to products of hydrolysis of the catalyst 1tsel f. It is imwhich were added 0.5 ml. N-methylmorpholine or a portant to note that-sodium dicyanamide improves the similar quantity of another tertiary amine, p.15 moisture resistance in every case.

' Table I i Foam Properties Percent Modulus Lost Alter Aging at 70 0. over Water NaN(ON)z yst v a :Parts/IUO h -p'o1yester Density; L25, l 2 3 4 5 6 7 8 9 lbs/it. lbs/in. Week Weeks Weeks Weeks Weeks Wee-its Weeks Weeks Weeks cantons.-. r o as 0.99 10 as 00 71 N-methyl morpholine 1 Part/100 8 16 32 37 Puma) 3. o 4. 2 0. s5 7 10 28 30 4.0 4.2 0. 74 9 17 25 31 5.0 as 0. 67 4 15 19 30 C p 2 0 I 1 3% 8- g2 13 f3 g? 2-H drox to l N- 3-dimethylariiinopr bgyl y carbiimate (0.6 g 1: 3g 2g Part/100 p y :0 3: 6 0: 62 6 1 24 35 cmnpmmdg 3 g; g; 22 :3 N N'-h xa .th 1 n0 di b.ta-

as.yiamfishifarbamt 2 9-3 3-3 3g 3, 13 g; g; parts/100 p y 9 52 5 8 27 Compound 4 0 g g? 32 100 R ti dtfdii "d timbfidlihhamhau 3-3 3-3 3-33 f3 33 (2 moles) to acid number of 25. 44 10 39 "-"s Principally the diester di-(diethyl 0 2 M 16 27 42 64 aminoethyl) adipate 0 n 33 1 Made with 80/20 mixture of 2,4/2,6 toluene diisocyenate isomers. L25 is the load in lbs/in. required to compress the foam 26%.

Emulphor EL-719, 1.0 ml. water and 0 to 2.5 grams dry, The above table shows the inhibiting effect of the compowdered sodium dicyanamide. These materials were pound sodium dicyanamide, NaN(CN) on accelerated then mixed for 5-10 seconds using a simple laboratory stirrer of the propeller type. Then 12.5 ml. (15 grams) of tolylene diisocyanate was added and mixing continued for 15-20 seconds. The mixer was withdrawn and the foam rose in about two minutes to a volume greater than that of the cups. The reaction was exothermic and degradation by moisture. The degree of inhibition is roughly proportional to the amount used.

Table II shows the beneficial efiect of NaN(CN) in retarding discoloration. These data were obtained on samples of compound 1, Table I, which had been in the fadeometer for 24 hours.

This example shows the effectiveness also of the dicyanamides of calcium, magnesium, barium and strontium (all alkali or alkaline earth metals), whereas the dicyan: amides of metals which are harmful per se, such as those of tin, zinc and lead, are shown to be unsatisfactory. The polyester employed is generally similar to that used in the prev ous example. The formulation of the foamed material was as follows:

Parts P ly 1.0. To y n s y n 3 Emulsifying agent (Emulphor EL-179) 0.3 N-methyl morpholine V g l Water V I v 2 M-dicyanarnide Variable The percent modulus lost after aging at 70 C. over water for various periods was determined, with the re-.

sults shown in Table. IH.

Table III- 7 Percent Modulus Lost Alter Aging at 70 C. over Water M P s 1 week 2 weeks 3 weeks 4 weeks While it is not desired to limit the invention to any particular theory of operation, it is interesting to note ,dicyanamide is sodium dicyanamide.

- 8 that the moisture-induced deterioration of ordinary polyester-urethane rubbers is apparently associated with hydrolysis of the ester groups and the urethane groups, since Brockhagen (Kunststofie 44, 555-8) found solublepolyester fragments in the degraded rubber. Thus, the polyester. used. in the above example degrades rapidlyat C. and slowly at room temperature if it contains water, and the amount of degradation depends on the-amount of Water added. Soaking samples. of polyester-urethane foam, in. bufiered. solutions showed that degradation was slow at pH 8-9 and very rapid at pH 274. However, materials which one would expect to neutralize any acid r a y p en r d that might be f me byhydrolysis did not, in general, have any beneficial effect as far as mitigation of such degradation was concerned. noted above, various metallic compounds proved to be no good, and in fact in some cases were harmful, and no benefit was derived from various organic acid acceptors, such as are used to stabilize polyvinyl chloride. The discovery of the effectiveness of metallic dicyanamides was therefore quite unexpected, as noted previously.

The. stabilized or preserved solid or foamed polyesterurethane rubber composition of the invention is useful inmany applications, such as the manufacture of tires, hose, belts and various other mechanical rubber goods, as well as cushions, mattresses, etc., and is a decided improvement over unstabilized polyester-urethane rubber for use in such applications.

H ing. thu r bed y invention, ha I l m and desire to protect by Letters Patent is:

l. "A polyester-polyurethane polymer containing at l astQ-l p t by Weight, p r p rts of aid p ym of a metallic dicyanarnide selected from the group consisting: of alkali and alkaline earth metal dicyanarnides, said polymer being a reaction product of an organic po y s'oe 'n e S ec d r t e group o sist of d isocyana'tes and triisocyanates with a polyester which is a reaction product of a glycol and a dicarboxylic acid.

2. A foamed rubbery polymer as in claim 1.

3. A polymer as in claim 1, in which the metallic 4. A foamed rubbery polymer as in claim 3.

References Cited in the file of this patent I UNITED STATES PATENTS Hopp a a1. eb- 5., 1251 

1. A POLYESTER-POLYURETHANE POLYMER CONTAINING AT LEAST 0.1 PART BY WEIGHT, PER 100 PARTS OF SAID POLYMER, OF A METALLIC DICYANAMIDE SELECTED FROM THE GROUP CONSISTING OF ALKALI AND ALKALINE EARTH METAL DICYANAMIDES, SAID POLYMER BEING A REACTION PRODUCT OF AN ORGANIC POLYISOCYANATE SELECTED FROM THE GROUP CONSISTING OF DIISOCYANATES AND TRIISOCYANATES WITH A POLYESTER WHICH IS A REACTION PRODUCT OF A GLYCOL AND A DISCABOXYLIC ACID.
 2. A FOAMED RUBBERY POLYMER AS IN CLAIM. 